Overbased bridged phenol metal salt/halo carboxylic acid condensate additives for lubricants

ABSTRACT

Compositions made by reacting (I) a metal phenoxide salt of a bridged phenol of 2 to about 20 phenol groups and (II) a carboxylic acid reagent containing from one to three carboxyl-based groups and a halogen-substituted hydrocarbon-based aliphatic or alicyclic group containing a halogen atom are useful as additives for lubricants and normally liquid fuels. Analogous thiophenoxide-based compositions are similarly useful. These compositions can also be used as intermediates for the preparation of other useful additive compositions through their reaction with alcohols, amino compounds, reactive small ring heterocycles and basically reacting metal compounds.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 608,380filed Aug. 27, 1975 now U.S. Pat. No. 4,067,698.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to additive compositions for use in lubricantsand normally liquid fuels. More particularly, it relates to compositionsprepared by reacting metal phenoxide salts of bridged phenols withcarboxylic acid reagents having halogen-bearing aliphatic or alicyclicgroups. The invention also pertains to oil-based lubricant, normallyliquid fuel and additive concentrate compositions containing theseadditive compositions. Products of the post-treatment of thesecompositions with amines, alcohols, small ring heterocycles and metalsalts are also useful as additives for oil-based lubricants and normallyliquid fuels and are within the scope of this invention as are fuel,lubricant and concentrate compositions containing them.

2. Prior Art

Nonylphenoxy acetic acid is known as an effective anti-corrosion agentfor a variety of petroleum-based fluids and synthetic lubricants such assilicones. See for example, "Corrosion", Volume 16, pages 17-19 (1960).

Certain imidazoline or diamine salts of alpha substituted acetic acidsof the formula:

    R.sup.0 XCH.sub.2 COOH

wherein X is oxygen, sulfur or an amino group, and R⁰ is an alkaryl,etc., group, are described as anti-corrosion agents for lubricants andnormally liquid fuels in U.S. Pat. No. 3,775,320.

3. General Background

The ability of a lubricant or normally liquid fuel to inhibit corrosionof metals with which it comes in contact is becoming an increasinglysought-after property in these days of material shortages, spiralingequipment replacement costs, and environmental consciousness. Suchanti-rust and/or anti-corrosion properties are usually enhanced inlubricants or normally liquid fuels through use of additive organiccompounds.

The ability of lubricants and normally liquid fuels to remove from metalsurfaces and disperse sludge which accumulates during storage or use ofa lubricant or fuel is also a highly desirable property since it allowsmore efficient utilization of the lubricant or fuel and preventsequipment breakdowns and deterioration. It is also desirable for a fuelor lubricant to possess properties which prevent or at least inhibit theaccumulation of varnish (resinous oxidation products) on interior engineparts such as pistons, cylinder walls and the like. Such properties arealso usually obtained through the addition of organic additives to thelubricant or fuel.

The compositions of this invention and post-treated compositions madefrom them are useful as anti-rust and anti-corrosion additives and canimpart useful detergent, dispersant, and varnish-inhibiting propertiesto compositions containing them.

4. Objects

Therefore, it is an object of this invention to provide additivecompositions that will impart useful and desirable properties tooil-based lubricants and normally liquid fuels containing them. Morespecifically, it is an object of this invention to provide compositionsthat will function in lubricants and fuels as anti-rust, anti-corrosion,anti-sludge or varnish-inhibiting agents. It is a further object toprovide novel concentrates, lubricants and fuels containing the additivecompositions. Other objects will be apparent to those skilled in the artupon review of this specification.

SUMMARY OF THE INVENTION

The above-stated objects are accomplished with the present invention byreacting (I) at least one phenoxide metal salt of a bridged phenolhaving (a) at least 2 and up to about 20 phenolic moieties or thiophenolanalogs thereof and (b) at least 1 to about 19 bridging linkagesindependently selected from the group consisting of covalentcarbon-to-carbon single bonds, ether linkages, sulfide linkages,polysulfide linkages of two to six sulfur atoms, sulfinyl linkages,sulfonyl linkages, methylene linkages, alkylene linkages, di(loweralkyl)methylene linkages, lower alkylene ether linkages, lower alkylenesulfide linkages, lower alkylene polysulfide linkages of two to sixsulfur atoms, amino linkages, polyamino linkages and mixtures of saiddivalent bridging linkages with (II) at least one carboxylic acidreagent having 1 to about 3 carboxyl-based groups and ahalogen-substituted hydrocarbon-based aliphatic or alicyclic groupcontaining a halogn atom.

Post-treated compositions made by further reaction of these inventivecompositions with mono- or polyhydric alcohols, basically reacting metalcompounds, amino compounds such as mono-amines, hydrazines,hydroxyamines, polyamines, hydroxypolyamines and small ring heterocyclesare also within the scope of the invention as are lubricants, normallyliquid fuel and additive concentrates containing these compositions andpost-treated compositions.

DETAILED DESCRIPTION OF THE INVENTION

(I) The phenoxide metal salt of a bridged phenol:

The bridged metal phenoxides used in the present invention have (a) atleast 2 and up to about 20 phenolic moieties or thiophenol analogsthereof and (b) at least 1 to about 19 bridging linkages independentlyselected from the group consisting of covalent carbon-to-carbon signalbonds, ether linkages, sulfide linkages, polysulfide linkages of two tosix sulfur atoms, sulfinyl linkages, sulfonyl linkages, methylenelinkages, alkylene linkages, di(lower alkyl)methylene linkages, loweralkylene ether linkages, lower alkylene sulfide linkages, lower alkylenepolysulfide linkages of two to six sulfur atoms, amino linkages,polyamino linkages and mixtures of said divalent bridging linkages.

The terms "phenol", "phenolic", "phenoxide", etc. are used in thisspecification in a generic sense to signify a hydroxy aromatic compoundhaving one or more (fused if more then one ring) carbocyclic rings and ahydroxyl group (or salt thereof) bonded direct to a ring carbon.Generally, the phenolic moieties of the bridged phenoxides used in thisinvention have mononuclear or fused binuclear aromatic rings having 6 or10 carbon atoms and are hydrocarbon-based in the sense discussed below.

Preferably, the phenoxide metal salts of this invention contain one ormore phenolic moieties substituted with 1 to 3, preferably 1,hydrocarbon-based aliphatic or alicyclic groups of from 1 to about 300,preferably about 30 to about 250, carbon atoms.

As used herein, and in the appended claims, the term "hydrocarbon-basedgroup" denotes a group directly bonded through carbon atom to anotherportion of the molecule (e.g., in (I), an aromatic nucleus) and having apredominately hydrocarbon character within the context of thisinvention. Such groups include the following:

(1) Purely hydrocarbon groups, that is, aliphatic (e.g., alkyl oralkenyl), or alicyclic (e.g., cycloalkyl or cycloalkenyl), and the like,as well as cyclic groups wherein the ring is completed through anotherportion of the molecule (that is, any two indicated substituents maytogether form an alicyclic group or aliphatic- or alicyclic-substitutedgroups). Such groups are known to those skilled in the art; examplesinclude (in addition to those noted hereinafter) C₃₀ H₆₁ --(allisomers), C₄₀ H₇₉ --(all isomers), ##STR1##

(2) Substituted hydrocarbon groups, that is, groups containingnon-hydrocarbon substituents which, in the context of this invention, donot alter the predominantly hydrocarbon character of the group. Thoseskilled in the art will be aware of suitable substituents which includegroups and atoms such as:

pendant ether substituents (especially hydrocarbyloxy and particularlyalkoxy substituents of up to ten carbon atoms);

pendant thioether substituents (especially C₁ -₁₀ alkyl thioethers suchsas methylmercapto, butylmercapto, etc.)

pendant oxo groups (especially ##STR2## pendant hydrocarbyl sulfonylsubstituents (--SO₂ R" where R" is a C₁ -₁₀ hydrocarbyl group)

pendant carbo-oxyhydrocarbyl (e.g., --C(O)OR", R" being as above) andthe analogous acyloxyhydrocarbyl substituents (e.g., --O(O)CR", R" beingas above) pendant sulfinyl substituents (--S(O)R", R" being as above)

Many other such non-hydrocarbyl substituents will be apparent to thoseskilled in the art.

Also included within the scope of substituted hydrocarbon groups for thepurpose of describing this invention are hydrocarbon groups havinglinkages in their main chains analogous to the pendant ether, thioether,oxo, sulfonyl and sulfinyl substituents described immediatelyhereinabove.

(3) Hetero groups; that is, groups which while predominately hydrocarbonin character within the context of this invention, contain atoms otherthan carbon present in a ring otherwise composed of carbon atoms.Suitable hetero atoms will be apparent to those skilled in the art andinclude, for example, oxygen, sulfur (in both its oxidized andunoxidized forms) phosphorus and nitrogen. Such hetero groups include,for example, furyl, thienyl, pyranyl, pyrrolyl, dihydro-imidazolyl,pyridyl, pyrazolyl; pyrazolinyl, indolyl, piperidyl, piperazinyl,morpholinyl, morpholino, and their hydrocarbon substituted analogs(e.g., 4-n-hexyl pyridinyl).

In general, the hydrocarbon-based groups of the phenoxide moieties ofthe salts used in this invention contain no more than about three of thehereinabove-described non-hydrocarbon substituents or hetero atoms, andpreferably, no more than one for each 10 carbon atoms in thehydrocarbon-based group. They also in general contain no more than oneunsaturated carbon-to-carbon linkage per every 10 saturatedcarbon-to-carbon linkages.

Generally, the hydrocarbon-based group in the phenoxide moieties of thesalts used in this invention are purely hydrocarbyl and aliphatic oralicyclic in nature. Preferably, they are purely aliphatic in nature andmore preferably, they are saturated aliphatic groups (i.e., containingno more than 1 carbon-to-carbon unsaturated linkage for every 20carbon-to-carbon single bond linkages.)

The sources of the hydrocarbon-based groups include principally the highmolecular weight substantially saturated petroleum fractions andsubstantially saturated olefin oligomers and polymers, particularlyoligomers and polymers of mono-olefins having from 2 to about 30 carbonatoms. The especially useful polymers are the homopolymers of1-mono-olefins such as ethylene, propene, 1-butene, isobutene, 1-hexene,1-octene, 2-methyl-1-heptene, 3-cyclo-hexyl-1-butene,2-methyl-5-propyl-1-hexene, 1-dodecene, 1-tetradecene, 1-octadecene,1-cosene, 1-tetracosene, etc.

Homopolymers of medial olefins, i.e., olefins in which the olefiniclinkage is not at the terminal position, likewise are useful. They areillustrated by 2-butene, 3-pentene, and 4-octene. Mixtures of thesehomopolymers such as a mixture of poly(propene) and poly(1-decene) canalso serve as the source of the hydrocarbon-based groups.

Also useful are the interpolymers of the olefins, such as thosementioned above with other interpolymerizable olefinic substances suchas aromatic olefins, cyclic olefins, and polyolefins. Such interpolymersinclude, for example, those prepared by polymerizing isobutene withstyrene; isobutene with butadiene; propene with isoprene; ethylene withpiperylene; isobutene with 1-tetradecene; isobutene with p-methylstyrene; 1-hexene with 1,3-hexadiene; 1-octene with 1-hexene; 1-heptenewith 1-pentene; 3-methyl-1-butene with 1-octene; 3-3-dimethyl-1-pentenewith 1-hexene; isobutene with styrene and piperylene; etc.

Mixtures of such interpolymers as well as mixture of one or moreinterpolymer with one or more hompolymer can also serve as the source ofthe hydrocarbon-based group.

Specific examples of such interpolymers include copolymer of 95% (byweight) of isobutene with 5% of styrene; terpolymer of 98% of isobutenewith 1% of piperylene and 1% of chloroprene; terpolymer of 95% ofisobutene with 2% of 1-butene and 3% of 1-hexene; terpolymer of 60% ofisobutene with 20% of 1-pentene and 20% of 1-octene; copolymer of 80% of1-hexene and 20% of 1-heptene; terpolymer of 90% of isobutene with 2% ofcyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20%of propene. Especially preferred sources of the hydrocarbon-based groupsof this invention are homo- and interpolymers of the various butenes(i.e., isobutene, 1- and 2- butene and mixtures thereof). Particularlypreferred sources are such butene polymers wherein isobutene units##STR3## predominate, preferably to the extent of about 80% of the unitsin the molecule. Other preferred polymers are C₃ -₁₆ alpha olefinpolymers and interpolymers including ethylene interpolymers.

Another source of the hydrocarbon-based groups are saturated aliphatichydrocarbons such as highly refined high molecular weight white oils orsynthetic alkanes such as are obtained by hydrogenation of the highmolecular weight olefin polymers discussed above or other high molecularweight olefinic substances. Halogenated analogs (particularlychlorinated and brominated analogs) of the hydrocarbon group sourcesjust discussed can also serve as sources of the hydrocarbon-based groupsin the phenol moieties of the bridged phenoxides of this invention.

The use of olefin polymers having number average molecular weights ofabout 750-5000 is preferred (as measured by gel permeationchromatography or vapor pressure osmometry).

A preferred class of bridged phenols that can be used in the presentinvention is represented by the general formula: ##STR4## wherein n, n'and n" are each independently integers of 1-3 but preferably 1 each; R,R' and R" are each independently aliphatic hydrocarbon-based groups,generally, alkyl or alkenyl groups, of one to about 300 carbon atoms,preferably about 6 to 200 carbon atoms each, and usually about 30 to 250carbon atoms each; m, m' and m" are each independently integers of 0-3,but generally 1 or 2 each; N is an integer of 0-20 but usually 0-5; andX is a divalent bridging linkage selected from the group consisting ofcovalent carbon-to-carbon single bonds, ether linkages, sulfidelinkages, polysulfide linkages of two to six sulfur atoms, sulfinyllinkages, sulfonyl linkages, methylene linkages, alkylene linkages,di(lower alkyl)methylene linkages, lower alkylene ether linkages, loweralkylene sulfide linkages, lower alkylene polysulfide linkages of two tosix sulfur atoms, amino linkages, polyamino linkages and mixtures ofsaid divalent bridging linkages. The divalent bridging linkage morepreferably will be a lower alkylene linkage of up to seven carbon atoms,and particularly preferably a methylene linkage, --CH₂ --, or a sulfideor polysulfide radical of the general formula --S_(z) -- where z has anaverage value of 1 to 6, usually 1 to 4. The bridging can also be adivalent amino-containing radical of the formulae such as ##STR5## wherethe alkylene groups are lower alkylene of 1 to about 10 carbons, usuallymethylene, R₁ is hydrogen or lower alkyl group, and R₂ is a divalenthydrocarbon group having up to seven carbon atoms, usually an alkylenegroup.

These bridged phenols and their neutral and basic metal salts are knownand can be prepared by many conventional processes as shown by thefollowing U.S. Patent numbers which are expressly incorporated herein byreference for their disclosure of the preparation of various bridgedphenols and their metal salts:

    ______________________________________                                        2,250,188      2,472,518                                                                              3,014,868                                             2,280,419      2,647,873                                                                              3,057,800                                             2,340,036      2,680,097                                                                              3,259,551                                             2,375,222      2,711,947                                                                              3,336,226                                             2,410,911      2,725,358                                                                              3,338,063                                             2,415,833      2,736,701                                                                              3,429,812                                             2,445,736      2,786,030                                                                              3,454,497                                             2,445,737      2,810,697                                                                              3,474,035                                             2,459,113      2,833,719                                                                              3,539,633                                             2,459,114      2,920,105                                                                              3,793,201                                             2,472,517      2,957,908                                                                              3,873,627                                             ______________________________________                                    

Among the preferred metal salts of bridged phenols are those selectedfrom the class of neutral metal salts of the condensation products ofaliphatic hydrocarbon-substituted phenols and lower aliphatic aldehydescontaining up to seven carbon atoms. The aliphatic hydrocarbonsubstituents on the phenols used in preparing such condensation productsshould provide a total of at least six aliphatic carbon atoms permolecule of phenol and preferably, a total of at least eight aliphaticcarbon atoms per molecule. Each aliphatic hydrocarbon substituent maycontain from about four to about 250 or more aliphatic carbon atoms butgenerally will contain from about six to about 100 aliphatic carbonatoms. The aliphatic aldehyde used in the formation of these phenolaldehyde condensation products is preferably formaldehyde or a reactiveequivalent thereof such as formalin, trioxane or paraformaldehyde. Othersuitable aldehydes include acetaldehyde, crotonaldehyde, butyraldehyde,propionaldehyde, and the like. Examples of the preparation of the metalsalts of phenol-aldehyde condensation products is found in many of theabove-incorporated patents, for example, U.S. Pat. No. 2,647,873.

Methods for making the metal phenoxides from the corresponding phenolsare well known to those of skill in the art and need not be dealt within detail here. For example, phenoxides can be produced by reaction ofthe pure metal or a hydroxide, oxide or hydride thereof, with the freephenols.

Methods for attaching hydrocarbon-based groups to the aromatic nuclei ofbridged phenoxides (or phenol precursors) are equally well known in theart. For example, the production of phenols substituted withaliphatic-based groups is described in the article entitled "Alkylationof Phenols" in Kirk-Othmer "Encyclopedia of Chemical Technology", SecondEdition, Volume 1, pages 894-895, Interscience Publishers a division ofJohn Wiley and Company, 1963. Other equally appropriate and conveninettechniques for the production of phenoxides useful in this inventionwill occur readily to those skilled in the art. The hydrocarbon groupscan be introduced either before or after introduction of the bridginglinkages between the phenolic nuclei. Preferably, however, they areintroduced before.

(II) The carboxylic acid reagent.

The carboxylic acid reagents used to produce the additive compositionsof the present invention have 1 to 3 carboxyl-based groups, and containa halogen-substituted hydrocarbon-based aliphatic or alicyclic group,that is a group having a halogen atom attached directly to an aliphaticor alicyclic carbon atom, i.e., a carbon atom that is part of analiphatic or alicyclic group. The use of these terms does notnecessarily mean that the carboxylic acid reagent is solely or evenpredominantly aliphatic or alicyclic in character. For example,1-chloro-1-phenyl acetic acid contains a chlorine atom attached to analiphatic carbon atom (i.e., the benzyl carbon atom), but thepredominance of carbon atoms in the molecule are aryl in nature.Similarly, 5-bromo-(1-naphthyl)3-cyclohexene carboxylic acid contains apredominance of aryl carbon atoms, but the bromine atom is attached toan alicyclic carbon atom.

Preferably, in these carboxylic acid reagents, the halogen atom ischlorine or bromine; generally, it is bonded to a carbon atom which isnot directly doubly bonded to another carbon atom. More preferably, thechlorine or bromine atom is bonded to a carbon alpha to at least one ofthe carboxyl-based groups present. There are one to three halogen atoms,preferably one, present in the acid reagent molecule.

Generally, these carboxylic acid reagents contain only carboxyl-basedgroups (as described hereinbelow) and the halogen-bearing and alicyclicgroup. Preferred reagents are of the formula

    A-(Cox).sub.1 -.sub.3

wherein A represents a halogenated, hydrocarbon-based aliphatic oralicyclic group of 1 to about 20 carbon atoms having a number ofunsatisfied valences corresponding to the number of Cox groups present,and each Cox independently represents a carboxyl-based group. Exemplaryof such A groups are chloro- and bromomethyl 1- and 2-chloro- andbromomethyl; 1-, 2- and 3-chloro- and bromopropyl, etc.; 1-, 2-, 3-etc., chloro-and bromocyclopentyl and cyclohexyl groups are alsoexemplary of the A group.

"Carboxyl-based" groups include free carboxylic acid groups, as well ascarboxylic anhydride groups, carboxylate groups of any of the metaldiscussed hereinabove in relation to the metal phenoxides, carboxylicacid ester groups of mono- and polyhydric alcohols as discussedhereinbelow and carboxylic acid nitrogen-containing groups such ascarboxamide and ammonium carboxylate groups of the amino compoundsdiscussed hereinbelow.

Means for obtaining carboxylic acid reagents useful in this inventionare well known to those of ordinary skill in the art. Many arecommercially available chemicals, others can be readily prepared fromsuch commercially available chemicals by reactions and techniques wellknown to the art. See, for example, Kirk-Othmer, "Encyclopedia ofChemical Technology", Second Edition, Volume 1, Pages 224 et seq., JohnWiley & Sons, Inc., N.Y., N.Y., 1965.

The preferred acid reagents are esters, amides and metal and/or ammoniumsalts; salts and esters are particularly preferred.

Generally, these preferred acid reagents have from 1 to 2 carboxyl-basedgroups and they are substantially free of ethylenic or acetylenicunsaturation (i.e., having no more than one such unsaturatedcarbon-carbon double bond for every 10 carbon-carbon single bonds).

The alcohols which can be used to form the ester carboxylic acidreagents useful in making the compositions of this invention can berelatively simple lower mono- or dihydric hydrocarbon-based alcoholssuch as methanol, ethanol, the propanols, butanols, pentanols, hexanols,heptanols, including both their aliphatic and alicyclic isomers;ethylene-, propylene-, butylene-, pentylene-, hexylene-, andheptylene-glycols wherein the 2 hydroxyls are separated by 2 carbonatoms; including both their aliphatic and alicyclic isomers are alsouseful. Tri-, tetra-, penta-, hexa-, and heptamethylene glycols andhydrocarbon-substituted analogs thereof containing a total of less than8 carbon atoms (e.g., 2-ethyl-1,3-trimethylene glycol, etc.) includingtheir alicyclic and aliphatic analogs can be used. Phenol and thevarious dihydric benzene compounds (e.g., resorcinol and thehydroquinones) as well as the various cresols and hydroxyl-substitutedcresols and benzyl alcohol and hydroxyl-substituted analogs thereofwhere the second hydroxyl group is directly bonded to an aromatic carbon(e.g., 3-HO-ΦCH₂ OH wherein Φ is a divalent benzene ring) can also beused. In this specification, the term "lower alcohols" refers toalcohols which contain one or two hydroxyl groups and one to sevencarbon atoms. Mono- and dihydric alkanols are preferred.

The carboxylic acid ester reagents useful in making the compositions ofthis invention can also be made from relatively higher mono- andpolyhydric hydrocarbon-based alcohols. In this specification, the term"higher alcohols" refers to alcohols which contain either 8 or morecarbon atoms and/or 3 or more (up to 8) hydroxyl groups. Preferably theycontain 8 to about 30 carbon atoms and 1 to about 6 hydroxyl groups. Thehigher alcohols can be aliphatic, alicyclic, mixed aliphatic alicyclic(e.g., pentyl cyclohexyl), aromatic (e.g., the naphthanols,benzohydroquinones, and phenylphenols), mixed aliphatic-aromatic (e.g.,beta phenyl ethanol, 3-phenyl propanol, etc. as well as the ethyl-,n-decyl-, n-pentadecyl-phenols, etc.) and alicyclic-aromatic (e.g., thecyclohexyl phenols, phenyl cyclohexanols, etc.) monohydric alcohols.

Exemplary of the monohydric higher alcohols are the octanols, nonanols,decanols, hexadecanols, etc. as well as the so-called fatty alcohols andtheir mixtures, excluding hexanols and heptanols, which are discussed indetail under the title "Higher Fatty Alcohols" in Kirk-Othmer,"Encyclopedia of Chemical Technology", Second Edition, John Wiley andSons, N.Y., 1965, Vol. 1, pages 542-557. Among such alcohols are thoseknown as lauryl, myristyl, cetyl, stearyl and behenyl alcohols.

Fatty alcohols containing minor amounts of unsaturation (e.g., no morethan two carbon-to-carbon unsaturated bonds per molecule) are alsouseful and are exemplified by palmitoleyl (C₁₆ H₃₂ O), oleyl (C₁₈ H₃₆ O)and eicosonyl (C₂₀ H₄₀ O) alcohols.

Higher synthetic monohydric (excluding C₆ and C₇ alcohols) alcohols suchas formed by the Oxo process (e.g., 2-ethyl hexyl), the aldolcondensation, and by aluminum organic (e.g., Aluminum triethyl)-catalyzed oligomerization of alpha olefins (especially ethylene)followed by oxidation are also useful. These higher synthetic alcoholsare discussed in detail in the hereinabove cited "Encyclopedia ofChemical Technology", Vol. 1, at pages 560-569, which is herebyincorporated by reference for disclosures relating to higher syntheticalcohols.

Higher polyhydric alcohols containing either more than seven carbonatoms or at least 3 hydroxyl groups (and preferably up to about 8hydroxyl groups) can also be used in making the ester carboxylicreagents of this invention. Preferably, these higher polyhydric alcoholshave both more than seven carbon atoms and at least 3 hydroxyls,although some of the dihydric glycol ethers (described hereinbelow)contain only 2 hydroxyl groups, but are nevertheless useful.

Among the higher hydrocarbon-based polyhydric alcohols are the sugaralcohols of the general formula HOCH₂ (CHOH)-- C₂ -₅ CH₂ OH such aserythritol, sorbitol, mannitol, etc., such sugar alcohols are describedin detail at pages 569-588 of Vol. 1 of the "Encyclopedia of ChemicalTechnology" referred to hereinabove.

The various methylol polyols such as pentaerythritol and its oligomers(tripentaerythritol, etc.) as well as polyols such as trimethylolethyloland trimethylolpropane are also useful.

The higher dihydric glycols of the general formula HO(Alk-O)₁ -₂₀ Hwherein the total number of carbon atoms in all the "Alk" groups isgreater than 7 and less than about 30, can also be used in making theester carboxylic acid reagents used in this invention. Exemplary of suchglycols are the tetra and higher ethylene glycols, tripropylene glycol,dibutylene glycol, dipentylene glycol, dihexylene glycol, diheptyleneglycol, and simple diols having greater than 7 carbon atoms such as2,2,4-trimethyl 1,3-pentanediol, 1,4-cyclohexane dimethylol and2,2,4,4-tetramethyl 1,3-cyclobutane diol. Various polymethylene diolssuch as 1,10-decamethane diol (i.e., 1,10-decanediol and its higherhomologs are also useful.

Mixtures of two or more of the hereinabove discussed lower and/or higheralcohols can also be used to make the carboxylic acid reagent and areoften preferred for reasons of economy and/or commercial availability.Generally, all isomers of the above-named alcohols are useful.

The carboxylic acid reagents used in this invention can be anitrogen-containing carboxylic acid reagent made from one or more aminocompounds. Generally, these amino compounds result in the carboxyl-basedgroup Cox being a carboxamide although more complex groups such ascarboximide ##STR6## or carboxamidine ##STR7## groups can be present.

Useful amino compounds from which the carboxylic and reagent can bederived are selected from the group consisting of amines, hydroxyamines, heterocyclic amines, polyamines, hydrazines, organicallysubstituted hydrazines, hydroxyl amines, and ammonia. Among the aminesuseful in preparing the carboxylic acid reagents are monoamines. Themonoamines can be primary, secondary or tertiary. Preferably, however,they are primary or secondary, i.e., they contain a ##STR8## linkage;more preferably they contain a primary amino group. These amines aresubstituted with C₁ -C₃₀ hydrocarbyl groups, hydrocarbon-based groups orhydroxy-substituted hydrocarbyl groups. Generally, these groups eachcontain between 1 and 10 carbon atoms and are aliphatic in nature.

The hydrocarbyl groups of these monoamines can each be independentlyselected from aliphatic, alicyclic, aromatic groups (includingaliphatic- and alicyclic-substituted aromatic groups andaromatic-substituted aliphatic and alicyclic groups). Specifically amongthese amines, can be, for example, methyl amine, ethyl amine, diethylamine, 2-propyl amine, n-butyl amine, di-n-butyl amine, isobutyl amine,coco amine, stearyl amine, lauryl amine, dimethyl lauryl amine, diethyllauryl amine, oleyl amine, aniline, paramethyl aniline, diphenyl amine,benzyl amine, tolyl amine, methyl-2-cyclohexyl amine, etc. Mixtures ofsuch amines can also be used.

Among the hydroxy amines which can be used to make the carboxylic acidreagents of the present invention are thehydroxy-hydrocarbyl-substituted analogs of the afore-describedmonoamines such as ethanol amine, di-3-propanol amine, 4-hydroxybutylamine, triethanol amine, n-methyl-2-propyl amine, 3-hydroxy aniline,etc. While it is preferred that such hydroxy amines contain only onehydroxyl group per molecule, those containing more, such as diethanolamine and tris(hydroxymethyl)methyl amine are also suitable for use inthis invention. Naturally when such hydroxy amines are used, thecarboxyl acid reagent can comprise mixtures of esters and ammoniumcarboxylates and/or carboxamides. Such mixtures are useful in thisinvention.

Heterocyclic amines are also useful in preparing the acid reagents (II)used to make the compositions of this invention. The cycle can alsoincorporate unsaturation and can be substituted with alkyl, alkenyl,aryl, alkaryl or aralkyl groups. In addition the cycle can also containother heteroatoms such as oxygen and sulfur or other nitrogen atomsincluding those not having nitrogen atoms bonded to hydrogen atoms.Generally, these cycles have 3 to 10, preferably 5 to 6 ring members.Among such heterocycles are substituted and unsubstituted aziridines,azetidines, azolidines, tetra- and dihydropyridines, pyrroles,piperidines, imidazoles, indoles, di- and tetrahydroimidazoles,piperazines, isoindoles, purines, morpholines, thiomorpholines,N-aminoalkyl morpholines, N-aminoalkyl thiomorpholines, azepines,azocines, azoinines, azecinines and tetra-, di- and perhydro-derivativesof each of the above.

Polyamides are also useful in preparing nitrogen-containing carboxylicacid reagents useful in this invention. Among these polyamines arealkylene polyamines including those conforming in the most part to theformula ##STR9## wherein a is an average of integers between 1 and about10, preferably between 2 and 8; each A is independently a hydrogen atom,a hydrocarbyl group or a hydroxy-substituted hydrocarbyl group having upto about 30 atoms. Generally A is an aliphatic orhydroxysubstituted-aliphatic group of up to about 10 carbon atoms."Alkylene" is an alkylene group having between 1 and 10, preferably 2 to6, carbon atoms. Especially preferred are the alkylene polyamines whereeach A is hydrogen with such ethylene polyamines being the mostpreferred. Such alkylene amines include ethylene polyamines, butylenepolyamines, propylene polyamines, pentylene polyamines, hexylenepolyamines, heptylene polyamines, etc. (wherein successive amino groupsare separated by two carbon atoms). The higher homologs of such aminesand related heterocyclic amines such as piperazines andaminoalkyl-substituted piperizines are also included. Polymethyleneamines (e.g., trimethylene amine) are also useful in making carboxylicacid reagents.

Polyamines useful in this invention are exemplified specifically by:ethylene diamine, triethylene tetramine, tetraethylene pentamine,pentaethylene hexamine, tris(2-aminoethyl)amine, propylene diamine,trimethylene diamine, decamethylene diamine, octamethylene diamine,di(heptamethylene)amine, propylene diamine, di(heptamethylene)triamine,tripropylene tetramine, di(trimethylene)triamine,2-heptyl-3-(2-aminopropyl)imidazoline, 4-methylimidazoline,1,3-bis-(2-aminoethyl)imidazoline, pyrimidine,1-(2-aminopropyl)piperazine, 1,4-bis(2-aminoethyl)piperazine,2-methyl-1-(2-aminobutyl) piperazine, etc. Higher homologs are obtainedby condensing two or more of the above-illustrated alkylene amines arelikewise useful as are mixtures of two or more of the afore-describedpolyamines.

Ethylene polyamine, as mentioned above, is especially useful for reasonsof cost and effectiveness. Such polyamines are described in detail inthe above-cited "Encyclopedia of Chemical Technology", Second Edition,Volume 7, pages 22-93. Such compounds are prepared most conveniently bythe reaction of an alkylene chloride with ammonia or by reaction of anethylene imine with a ring-opening reagent such as ammonia, etc. Thesereactions result in the production of the somewhat complex mixtures ofalkylene polyamines, including cyclic condensation products such aspiperazines. These mixtures are particularly useful in preparing thecarboxylic acid reagents of this invention. On the other hand, quitesatisfactory products can also be obtained by the use of pure alkylenepolyamines.

Hydroxyalkyl-substituted alkylene polyamines, i.e., alkylene polyamineshaving one or more hydroxyalkyl substituents on the nitrogen atoms,likewise are useful in preparing the carboxylic acid reagents of thisinvention. Preferred hydroxyalkyl-substituted alkylene polamines arethose in which the hydroxy alkyl group is a lower hydroxy alkyl group,i.e., having less than about 10 carbon atoms. Examples of suchhydroxyalkyl-substituted polyamines include N-(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)ethylene diamine,1-(2-hydroxyethyl)piperazine, monohydroxypropyl-substituted diethylenetriamine, 1,4-bis(2-hydroxypropyl)piperazine,di-hydroxypropyl-substituted tetraethylene pentamine,N-(3-hydroxybutyl)tetramethylene diamine, etc.

Higher homologs such as are obtained by condensation of theabove-illustrated alkylene amines or hydroxy alkylsubstituted alkyleneamines through amino radicals or through hydroxy radicals as well asmixtures of the above are likewise useful.

Useful carboxylic acid reagents can also be prepared from hydrazine oran organo-substituted hydrazine of the general formula ##STR10## whereineach Q is independently hydrogen or a C₁ -C₃₀ hydrocarbon-based group.Generally, at least one Q is a hydrogen atom and the other Q groups areC₁ -C₁₀ aliphatic groups. More preferably at least two Q groups arehydrogen. Most preferably, at least two Q groups are hydrogen and theremaining Q groups are alkyl of up to ten carbon atoms.

Examples of substituted hydrazines are methylhydrazine,N,N-dimethylhydrazine, N,N'-dimethylhydrazine, phenylhydrazine,N-phenyl-N'-ethylhydrazine, N-(p-tolyl)-N'-(n-butyl)hydrazine,N-(p-nitrophenyl)-N-methylhydrazine, N,N'-di-(p-chlorophenyl)hydrazine,N-phenyl-N'-cyclohexylhydrazine, etc.

Useful carboxylic acid reagents can also be prepared from hydroxylamineor hydrocarbyl substituted hydroxylamine analogs of the general formula:##STR11## wherein the Q groups have the same meaning described above andthe same preferences are used in choosing them.

Preferred amino compounds for preparation of the nitrogen-containingcarboxylic acid reagents of this invention are lower amines having 1 to2 amino groups or 1 amino and 1 hydroxyl group and a total of up to 7carbon atoms per molecule, ammonia, hydrazine, hydroxylamine, and lowerhydrazines and hydroxylamines having a total of up to 7 carbon atoms anda total of up to 2 nitrogen atoms per molecule.

In addition to ammonia, hydrazine and hydroxylamine, or analogs thereof,suitable inorganic salts which yield free hydrazine or hydroxylamineunder the reaction conditions may also be used, such as hydrazinesulfate and hydroxylamine hydrochloride.

Mixtures of two or more of the afore-described amino compounds can alsobe used in making the compositions of this invention. It is preferredthat the amino compounds used have at least one H-N= linkage withintheir structure.

In the preferred carboxylic acid reagents (II) the halogen is chlorineor bromine, the carboxyl-based group Cox is selected from the groupconsisting of carboxylates of Group IA metals (particularlychloroacetate salts), esters of lower alkanols (particularlychloroacetate esters), carboxamides of lower alkyl monoamines andammonia, and carboxylates of lower alkyl monoamines and ammonia.

Among the particularly preferred carboxylic acid reagents used toproduce the compositions of this invention are alpha-halo carboxyl acidreagents having 2 to 20 carbon atoms and being aliphatic- oralicyclic-based, especially those in which Cox is an ester group of alower alkanol. Exemplary of such carboxylic acid reagents are:

chloroacetic acid

ethyl chloroacetate

methyl-7-bromo stearate

sodium 1,1-di-chloropropionate

di(methyl)-1-chlorosuccinate

potassium phenyl chloroacetate

di(tetramethyl ammonium)-bromomalanate

calcium-bromo succinate

2-chloro-cyclohexanoic acid methyl ester

3-chloro glutaric acid

hexyl-4-chloro hexanoate

8-chloro-methyl stearate

mono-chloroacetic acid ester of pentaerythritol

3-bromobutyramide

sodium chloroacetate

ethyl, naphthyl bromoacetate

chlorosuccinic anhydride

etc.

Other appropriate halo carboxylic acid reagents within the scope definedhereinbelow will readily occur to those skilled in the art.

Normally, the compositions of this invention are made by reacting anequivalent of phenoxide metal salt with an equivalent of carboxylic acidreagent. An equivalent of phenoxide is determined by dividing thephenoxide molecular weight by the number of phenoxide (i.e.,metal-neutralized aryl hydroxide) groups present. For example, disodiumbisphenol A phenoxide has two equivalents per mole, the mono lithiumsalt of hydroquinone phenoxide has one equivalent per mole, etc. Anequivalent of carboxylic acid reagents is determined similarly bydividing the reagent molecular weight by the number of aliphatic halogenatoms present. When only one such halogen is present in the carboxylicacid reagent the reagent's molecular weight is also its equivalentweight. While one to one equivalent proportions mentioned are normallyused, in certain circumstances (e.g., where it is desired to drive thereaction forward rapidly), it is possible to use up to a five-foldexcess (in terms of equivalents) of the acid reagent per equivalent ofphenoxide. It is also possible to use up to the molecular weight of thephenoxide salt. Thus reactant ratio of acid reagent to phenoxide rangesbetween about 1:20 to 5:1 acid reagent: phenoxide salt. Mixtures of twoor more acid reagents and/or phenoxide reagents can also be used.

The reaction of phenoxide metal salt and carboxylic acid reagent takesplace at temperatures ranging between about 15° C. to the decompositiontemperature of the reaction component having the lowest decompositiontemperature. Usually it is not necessary to carry out the reaction at atemperature in excess of about 300° C. Usually the lowest reactiontemperature is about 50° C. and the highest reaction temperature isabout 200° C.

The reaction occurs normally in about 0.1-24 hours. The shortestreaction time is usually about 0.25 hours and the longest about 10hours.

The reaction is often preferably carried out in the presence of asubstantially inert, normally liquid solvent/diluent such as arelatively low boiling petroleum cut such as naphtha, textile spirits,reformate, petroleum ether, kerosene, gasoline, diesel fuel, etc.,having a 90% boiling point of less than about 250° C. at 1 torr. Otherorganic solvents such as lower alkanols, glycols, benzene, xylenes,toluene, octanes, tetrahydrofuran, pyridine, ethylene glycol ethers(e.g., the commercial products sold under the trade names cellosolvesand diglymes) etc., can be used as the inert solvent/diluent. Often itis desirable to use one or more of the lubricating oils describedhereinbelow as an inert solvent/diluent for the reaction of thephenoxide and carboxylic acid reagent.

Recovery of the product from the phenoxide metal salt/carboxylic acidreagent can be accomplished by means well known to those skilled in theart such as distillation, crystallization, precipitation, dialysis,absorbtion, etc. Often it is not necessary to recover the product if itis to be post-treated as described hereinbelow. Sometimes when thecarboxylic acid reagent is a salt it is convenient to neutralize theproduct by the addition of an inorganic protonic acid (e.g., H₂ SO₄, H₃PO₄, HCl, HNO₃, etc.) before recovering or post-treating the product.

It is believed that the compositions of this invention formed byreaction of the metal phenoxide I and the carboxylic acid reagent IIhave predominance of ether linkages resulting from displacement of thehalogen atom of the carboxylic acid reagent with a phenoxide anion. Thisbelief is supported by the observation that significant amounts of metalhalide by-products are formed during the reaction of I with II. Theinvention, however, is in no way limited to such ether compositions andrelatively low amounts of products having other molecular structures maybe present in the compositions of this invention.

The following are specific illustrative examples of how to make theaforesaid invention and include the best mode of the inventionspresently known. In these examples, as well as this specification andappended claims, all percentages and parts are by weight and themolecular weights are number average molecular weights (Mn) asdetermined by gel permeation chromatography (GPC) or vapor phaseosmometry (VPO).

EXAMPLE 1

A mixture of 1120 parts of a poly(isobutene)-substituted phenol (Mn 960VPO), 200 parts of xylene, 300 parts of mineral oil and 14 parts of 50%aqueous sodium hydroxide solution is heated at 75° C. At 78° C., 29.7parts of paraformaldehyde is added, and the reaction mixture is heatedat reflux for 2.5 hours. An additional 66 parts of 50% aqueous sodiumhydroxide solution is added, and the mixture dried by azeotropicdistillation. At 73° C., 110 parts of ethyl chloroacetate is added andthe mixture is held at 130°-147° C. for 2.5 hours. At 60° C., 100 partsof a commercial mixture of alcohols containing approximately 61%isobutyl alcohol and 39% amyl alcohol, 10 parts of aqueous hydrochloricacid and 30 parts of water is added. The mixture is refluxed at105°-107° C. for one hour, then azeotropically dried. The mixture isstripped to 170° C. under vacuum and filtered. The filtrate contains thedesired product and 19.9% mineral oil.

EXAMPLE 2

A mixture of 412 parts of the product mixture of Example 1 and 55 partsof a 39.5% aqueous solution of tris(hydroxymethyl)amino methane isheated at 140°-152° C. for nine hours, then stripped at 166° C. undervacuum and filtered. The filtrate contains the product and has anitrogen content of 0.59%.

EXAMPLE 3

A mixture of 782 parts (0.5 equivalent) of the product solution ofExample 1, 276 parts of mineral oil and 30.7 parts (0.75 equivalent) ofa commercial ethylene polyamine mixture, wherein the amines have anaverage of three to ten nitrogen atoms per molecule, containing about34% nitrogen is heated at 160°-165° C. for five hours. The mixture isstripped to 170° C. under vacuum and filtered to yield an oil solutioncontaining 0.97% nitrogen

EXAMPLE 4

A mixture of 2366 parts of a poly(isobutene)-substituted phenol (Mn 1369VPO), 350 parts of toluene and 41.5 parts of paraformaldehyde is heatedat 79° C. At 85° C., 56 parts of 50% aqueous sodium hydroxide solutionis added and the reaction mixture is heated at reflux for three hours.The mixture is then dried by azeotropic distillation. At 142° C., 86parts of ethyl chloroacetate is added and the reaction mixture is cooledto 80° C., whereupon 250 parts of a commercial mixture of alcoholsdescribed in Example 1, 25 parts of aqueous hydrochloric acid and 60parts of water are added. The reaction mixture is refluxed at 89°-91° C.for four hours, then azeotropically dried. The mixture is stripped to170° C. under vacuum and 1000 parts of mineral oil is added. The productsolution, which contains 29.1% mineral oil, is obtained by filtration.

EXAMPLE 5

A mixture of 1601 parts (0.28 equivalent) of the product solution ofExample 4, 290 parts of mineral oil and 17.3 parts (0.42 equivalent) ofthe commercial ethylene polyamine mixture described in Example 3 isheated at 165°-190° C. for seven hours, then filtered to obtain thedesired product solution (60% solution in mineral oil, containing 0.29%nitrogen).

EXAMPLE 6

A mixture of 5600 parts of a poly(isobutene)-substituted phenol (Mn 885VPO), 1600 parts of xylene and 80 parts of 50% aqueous sodium hydroxidesolution is heated at 65° C. At 67° C., 148.5 parts of paraformaldehydeis added and the reaction mixture is heated at reflux for four hours. Acharge of 171 parts of flake sodium hydroxide and 60 parts of water ismade to the reaction mixture at 82° C. and then dried by azeotropicdistillation. At 70° C., 750 parts of a commercial mixture of alcoholsdescribed in Example 1 and then 524 parts of sodium chloroacetate areadded and the mixture is held at reflux (124°-126° C.) for 10.5 hours.The mixture is stripped to 168° C. and 1000 parts of mineral oil isadded. At 98° C., 500 parts of aqueous hydrochloric acid and 100 partsof water are added to the reaction mixture, which is refluxed for 2.5hours followed by azeotropic distillation. The mixture is stripped to170° C. under vacuum and 1200 parts of mineral oil is added. The desiredproduct solution (containing 27.1% mineral oil) is obtained uponfiltration.

EXAMPLE 7

A mixture of 912 parts of the oil-containing product solution of Example6, 250 parts of mineral oil and 27.2 parts (0.8 equivalent) ofpentaerythritol is heated at 175°-210° C. for three hours, then at222°-230° C. for 4.5 hours. The mixture is stripped at 230° C. undervacuum and filtered to yield an oil solution of the desired productsolution (58% in mineral oil).

EXAMPLE 8

A mixture of 912 parts of the oil-containing product solution of Example6, 200 parts of mineral oil and 68 parts (2.0 equivalents) ofpentaerythritol is reacted according to the procedure in Example 7 toyield a 60% solution of the desired product in mineral oil.

EXAMPLE 9

A mixture of 912 parts of the oil-containing product solution of Example6, 200 parts of mineral oil and 36.3 parts (0.3 mole) oftris(hydroxymethyl)aminomethane is heated at 220°-225° C. for six hours,then stripped at 160° C. under vacuum and filtered. The filtrate is anoil solution of the product containing 0.34% nitrogen.

EXAMPLE 10

A mixture of 912 parts of the oil-containing product of Example 6, 150parts of mineral oil, 150 parts of toluene and 57.6 parts of3-aminopropyl morpholine is heated at 141°-161° C. for 9.5 hours, thenstripped to 169° C. under vacuum. Filtration yields a 64% solution inmineral oil, containing 0.96% nitrogen, as the desired product solution.

EXAMPLE 11

A mixture of 912 parts of the oil-containing product of Example 6, 170parts of mineral oil, 150 parts of toluene and 24.6 parts (0.6equivalent) of the commercial ethylene polyamine mixture used in Example5 is heated at 134°-149° C. for six hours, then stripped to 161° C.under vacuum and filtered to yield the desired product solution (62%solution in mineral oil) containing 0.76% nitrogen.

EXAMPLE 12

A mixture of 912 parts of the oil-containing product solution of Example6, 150 parts of toluene, 150 parts of mineral oil and 33.2 parts (0.8equivalent) of a commercial ethylene polyamine mixture corresponding inempirical formula to pentaethylene hexamine is reacted according to theprocedure set forth in Example 11. The product solution contains 36.5%mineral oil and 0.99% nitrogen.

EXAMPLE 13

A mixture of 2205 parts of the oil-containing product solution ofExample 6, 518 parts of mineral oil, 250 parts of toluene and 82 parts(2.0 equivalents) of a commercial ethylene polyamine mixture used inExample 5 is reacted according to the procedure used in Example 11. Theproduct solution obtained contains 40% mineral oil and 0.98% nitrogen.

EXAMPLE 14

A mixture is prepared by the addition of 22 parts of carbon disulfideover a period of three hours to 1100 parts of the amide prepared inExample 13 at 128°-130° C. The reaction mixture is held at 160°-165° C.for six hours under nitrogen. Filtration yields a product containing39.2% mineral oil, 0.53% sulfur and 0.98% nitrogen.

EXAMPLE 15

A mixture of 882 parts of the oil-containing product of Example 6, 205parts of mineral oil and 30.7 parts (1.0 equivalent) of glycerol isheated at 195°-210° C. for twelve hours under nitrogen. The mixture isstripped to 225° C. under vacuum and filtered. The filtrate is thedesired product solution (60% solution in mineral oil).

EXAMPLE 16(A)

A mixture is prepared by the addition of 60 parts of aqueoushydrochloric acid to 3880 parts of a poly(isobutene)-substituted phenol(Mn 885 VPO), 1500 parts of xylene and 108 parts of paraformaldehyde at75° C. The reaction mixture is dried by azeotropic distillation to yield5231 parts of the desired product solution.

EXAMPLE 16(B)

A mixture of 3160 parts of the product solution of Example 16, 100 partsxylene and 93 parts (2.25 equivalents) of sodium hydroxide is heated toreflux and azeotropically dried. The resulting phenoxide-containingmixture is cooled to 85° C. and 233 parts (2.0 equivalents) of sodiumchloroacetate is added followed by the addition of 500 parts of acommercial mixture of alcohols described in Example 1. The mixture isheld at reflux (119°-120° C.) for 6.5 hours and then stripped to 169° C.under nitrogen. After cooling the mixture to about 75° C., 400 parts ofwater, 300 parts of textile spirits and 450 parts of aqueoushydrochloric acid are added. The reaction mixture is stripped to 105° C.in four hours, refluxed at 105°-110° C. for four hours and then strippedto 174° C. under vacuum. Diluent oil, 500 parts, is added and themixture is filtered to yield 3178 parts of an oil solution of thedesired product.

EXAMPLE 17

A mixture of 862 parts of the oil-containing product solution of Example16(B), 150 parts of mineral oil, 200 parts of toluene and 21.5 parts(0.525 equivalent) of the commercial ethylene polyamine mixutre used inExample 5 is reacted according to the procedure described in Example 11.The product solution obtained contains 39% mineral oil and 0.72%nitrogen.

EXAMPLE 18

A mixture is prepared by the addition of 24 parts of aqueoushydrochloric acid to 798 parts of tetrapropenylsubstituted phenol, 300parts of xylene and 45 parts of paraformaldehyde at 65° C. The reactionmixture is held at 100°-107° C. for three hours, then dried byazeotropic distillation. The reaction mixture is cooled to 35° C. and256 parts of 50% aqueous sodium hydroxide solution is added. The mixtureis heated to reflux and azeotropically dried. At 62° C., 130 parts oftoluene, 360 parts of a commercial mixture of alcohols described inExample 1 and 349.5 parts (3.0 equivalents) of sodium chloroacetate areadded. The mixture is refluxed at 114° C. for 7.5 hours, stripped to162° C. and then 550 parts of mineral oil is added. After cooling to120° C., 400 parts of toluene, 500 parts of aqueous hydrochloric acidand 250 parts of water are added. The mixture is stirred at 65° C. forthree hours, stripped to 101° C., azeotropically dried and then strippedto 165° C. under vacuum. Filtration yields the desired oil-containingproduct solution.

EXAMPLE 19

A mixture of 385 parts of the oil-containing product solution of Example18, 50 parts of mineral oil, 75 parts of toluene and 43 parts (1.05equivalents) of the ethylene polyamine mixture used in Example 5 isreacted according to the procedure described in Example 11. The productsolution contains 40% mineral oil and 3.06% nitrogen.

EXAMPLE 20

A mixture is prepared by the addition of 19 parts ofpara-toluenesulfonic acid to 5600 parts of a poly(isobutene)-substitutedphenol (Mn 885 VPO), 1600 parts of xylene, 1200 parts of diluent oil and148.5 parts (4.5 equivalents) of paraformaldehyde at 65° C. The reactionmixture is heated at reflux for three hours, then cooled to 95° C. and216 parts (5.2 equivalents) of sodium hydroxide is added. The mixture isheated to reflux and dried by azeotropic distillation. The resultingphenoxide-containing mixture is cooled to 85° C. and 760 parts of acommercial mixture of alcohols described in Example 1 is added followedby the addition of 524 parts (4.5 equivalents) of sodium chloroacetate.The mixture is held at reflux (124°-126° C.) for seven hours and thenstripped to 172° C. under nitrogen. After cooling to about 99° C., 250parts of water, 1000 parts of mineral oil and 500 parts of aqueoushydrochloric acid are added. The reaction mixture is stripped to 163° C.under vacuum and filtered to yield 7384 parts of the desiredoil-containing product solution.

EXAMPLE 21

A mixture of 890 parts of the oil-containing product solution of Example20 and 150 parts of mineral oil is heated to 100° C. and 26 parts ofethylene oxide is added over 1.4 hours. The reaction mixture is strippedto 224° C. under vacuum, then filtered to yield the desired ester in 63%solution mineral oil.

EXAMPLE 22

The procedure for Example 10 is repeated except the product of Example 6is replaced on an equivalent basis by the product of Example 20.

EXAMPLE 23(A)

A mixture of 5300 parts of tetrapropenyl-substituted phenol, 820 partsof sodium hydroxide and 2203 parts of mineral oil is heated to 160° C.and dried under nitrogen. At 160° C., 1030 parts of sulfur dichloride isadded slowly. The reaction mixture is held at 160° C. for one hour undernitrogen to yield the desired product solution.

EXAMPLE 23(B)

A mixture of 5376 parts of the oil-containing product solution ofExample 23, 750 parts of xylene and 249 parts of sodium hydroxide isdried by azeotropic distillation. At 70° C., 699 parts of sodiumchloroacetate and 1200 parts of a commercial mixture of alcoholsdescribed in Example 1 are added and the mixture is held at reflux (125°C.) for seven hours. At 100° C., 1000 parts of toluene, 588 parts ofaqueous hydrochloric acid and 1000 parts of water are charged and thereaction mixture is again refluxed for one hour and then stripped to160° C. under vacuum. The desired oil-containing product solution isobtained by filtration.

EXAMPLE 24

A mixture of 422 parts of the oil-containing product solution of Example23(A), 200 parts of xylene and 72 parts of 3-aminopropyl morpholine isheated at reflux for two hours, then stripped to 150° C. under vacuum.Filtration yields the desired product solution containing 23% mineraloil, 2.59% nitrogen and 3.15% sulfur.

EXAMPLE 25

A mixture of 2688 parts of the oil-containing product solution ofExample 23(A), 500 parts of xylene and 251 parts of sodium hydroxide isdried by azeotropic distillation. At 70° C., 699 parts of sodiumchloroacetate followed by 1200 parts of a commercial mixture of alcoholsdescribed in Example 1 are added and the mixture is held at reflux (130°C.) for eight hours. The mixture is stripped to 150° C. under vacuum. At90° C., 1000 parts of water, 1000 parts of toluene, and 588 parts ofaqueous hydrochloric acid are added to the reaction mixture, which isrefluxed for one hour, followed by stripping to 155° C. under vacuum.The desired product solution (containing 2.52% sulfur) is obtained byfiltration.

EXAMPLE 26

A mixture of 456 parts of the oil-containing product solution of Example25, 200 parts of xylene and 101 parts of 3-aminopropyl morpholine isreacted according to the procedure described in Example 24. Theoil-containing product solution obtained contains 3.59% nitrogen and2.29% sulfur.

EXAMPLE 27

A mixture of 3584 parts of the oil-containing product solution ofExample 23(A), 800 parts of xylene and 336 parts of sodium hydroxide isdried by azeotropic distillation. At 130° C., 981 parts of ethylchloroacetate and 600 parts of a commercial mixture of alcoholsdescribed in Example 1 are added and the mixture is held at reflux forone hour, stripped to 150° C. under nitrogen, and filtered. Thefiltrate, containing 3.11% sulfur, is the desired product solution.

EXAMPLE 28

A mixture of 2774 parts of the oil-containing product solution ofExample 27 and 300 parts of hydrazine monohydrate is stripped to 150° C.under vacuum and filtered yielding the desired product solution.

EXAMPLE 29

A mixture of 5376 parts of the oil-containing product solution ofExample 23(A), 1125 parts of mineral oil, 800 parts of xylene and 480parts of 37% aqueous formalin solution is heated to 65° C. At 70° C.,252 parts of sodium hydroxide is added and the reaction mixture is driedby azeotropic distillation. At 140° C., 735 parts of ethyl chloroacetateis added and the mixture is held at reflux for three hours, thenstripped to 150° C. under vacuum and filtered. The filtrate is thedesired product solution (63% solution in mineral oil, containing 3.23%sulfur).

EXAMPLE 30

A mixture of 950 parts of the solution described in Example 29, 200parts of mineral oil, 60 parts of polybutenyl succinic anhydride (Mn1000), 44 parts of calcium hydroxide, 250 parts of a commercial mixtureof alcohols described in Example 1, and 120 parts of water is heated atreflux for one hour then stripped to 150° C. under nitrogen. Aftercooling to 60° C., 628 parts of methanol, 20 parts of acetic acid and119 parts of calcium hydroxide are added. The reaction mixture is thenblown with carbon dioxide at 1 cfh for 1.5 hours. The mixture isstripped to 150° C. under vacuum and filtered to yield an oil solutionof the overbased desired product.

EXAMPLE 31

A mixture of 2240 parts of a poly(isobutene)-substituted phenol (Mn 885VPO), 650 parts of xylene, 750 parts of mineral oil and 83.4 parts ofsodium hydroxide is dried by azeotropic distillation. Sulfur dichloride(103 parts) is added at 146°-151° C. in two hours. The reaction mixtureis heated at 151°-153° C. for one hour, then cooled to 98° C. whereupon83.4 parts of sodium hydroxide and 26.4 parts of paraformaldehyde areadded. The reaction mixture is azeotropically dried. At 90° C., 500parts of a commercial mixture of alcohols described in Example 1followed by 210 parts of sodium chloroacetate are added and the mixtureis held at reflux (122°-134° C.) for 5.5 hours. The mixture is strippedto 154° C. and then cooled to 98° C. whereupon 200 parts of toluene, 100parts of water and 205 parts of aqueous hydrochloric acid are added. Thereaction mixture is refluxed for two hours, dried by azeotropicdistillation, stripped to 173° C. under vacuum and filtered to yield2770 parts of the desired product solution (containing 23.9% mineraloil).

EXAMPLE 32

A mixture of 844 parts of oil-containing product solution of Example 31,200 parts of mineral oil, 150 parts of toluene and 24.6 parts of thecommercial ethylene polyamine mixture used in Example 5 L is reactedaccording to the procedure described in Example 11. The product solutionobtained contains 38% mineral oil and 0.78% nitrogen.

EXAMPLE 33

A mixture of 844 parts of the oil-containing product solution of Example31, 160 parts of mineral oil, 150 parts of toluene and 57.6 parts of3-aminopropyl morpholine is reacted according to the procedure describedin Example 10. The product solution obtained contains 34% mineral oil,1.01% nitrogen, and 0.89% sulfur.

EXAMPLE 34

The procedure of Example 1 is repeated except the ethyl chloroacetate isreplaced by an equimolar amount of diethyl chlorosuccinate.

EXAMPLE 35

The procedure of Example 23(A) is repeated except that the product ofExample 23 is replaced by an equimolar amount of 2,2'-dihydroxybiphenylalkylated with Pbu (Mn 1000 VPO) using a Friedel-Crafts catalyst.

The compositions of this invention are useful in and of themselves asanti-rust and anti-corrosion agents for fuels and lubricants,particularly when they are free acids, esters of the afore-describedhigher alcohols, carboxiamides or ammonium carboxylates of theafore-described polyamines. These esters, carboxamides and carboxylatescan also function in fuels and lubricants as detergents and dispersantsfor sludge and varnish formed in internal combustion engines. Thus, fueland lubricant compositions are within the scope of the invention hereindisclosed.

The compositions of this invention can be employed in a variety oflubricants based on diverse oils of lubricating viscosity, includingnatural and synthetic lubricating oils and mixtures thereof. Theselubricants include crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines, such as automobile andtruck engines, two-cycle engines, marine and railroad diesel engines,and the like. They can also be used in gas engines, stationary powerengines, turbines and the like. Automatic transmission fluids, transaxlelubricants, gear lubricants, metal-working lubricants, hydraulic fluidsand other lubricating oil and grease compositions can also benefit fromthe incorporation therein of the compositions of the present invention.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as mineral lubricating oils such as liquid petroleumoils and solvent-treated or acid-treated mineral lubricating oils of theparaffinic, naphthenic or mixed paraffinic-naphthenic types. Oils oflubricating viscosity derived from coal or shale are also useful baseoils. Synthetic lubricating oils include hydrocarbon oils andhalosubstituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);poly(1-hexenes), poly(1-octenes), poly(1-decenes), etc. and mixturesthereof; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g.,biphenyls, terphenyls, alkylated polyphenyls, etc.); alkylated diphenylethers and alkylated diphenyl sulfides and the derivatives, analogs andhomologs thereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc. constitute another class of known syntheticlubricating oils. These are exemplified by the oils prepared throughpolymerization of ethylene oxide or propylene oxide, the alkyl and arylethers of these polyoxyalkylene polymers (e.g., methylpolyisopropyleneglycol ether having an average molecular weight of 1000, diphenyl etherof polyethylene gylcol having a molecular weight of 500-1000, diethylether of polypropylene glycol having a molecular weight of 1000-1500,etc.) or mono- and polycarboxylic esters thereof, for example, theacetic acid esters, mixed C₃ -C₈ fatty acid esters, or the C₁₃ Oxo aciddiester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids, alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.)with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol, etc.). Specific examples of these estersinclude dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate,dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctylphthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyldiester of linoleic acid dimer, the complex ester formed by reacting onemole of sebacic acid with two moles of tetraethylene glycol and twomoles of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as the polyalkly-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another usefulclass of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropylsilicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate,tetra(p-tert-butylphenyl)silicate,hexyl-(4-methyl-2-pentoxy)-disiloxane, poly(methyl)siloxanes,poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid,etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and rerefined oils, either natural or synthetic (aswell as mixtures of two or more of any of these) of the type disclosedhereinabove can be used in the lubricant compositions of the presentinvention. Unrefined oils are those obtained directly from a natural orsynthetic source without further purification treatment. For example, ashale oil obtained directly from retorting operations, a petroleum oilobtained directly from primary distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques are known to those of skill in the art such assolvent extraction, secondary distillation, acid or base extraction,filtration, percolation, etc. Rerefined oils are obtained by processessimilar to those used to obtain refined oils applied to refined oilswhich have been already used in service. Such rerefined oils are alsoknown as reclaimed or reprocessed oils and often are additionallyprocessed by techniques directed to removal of spent additives and oilbreakdown products.

In general, about 0.05-20.0, preferably 0.1-10 parts (by weight) of acomposition of this invention is dissolved or stably dispersed in 100parts of oil to produce a satisfactory lubricant. The invention alsocontemplates the use of other additives in combination with thecomposition of this invention. Such additives include, for example,auxiliary detergents and dispersants of the ash-producing or ashlesstype, oxidation inhibiting agents, pour point depressing agents, extremepressure agents, color stabilizers and anti-foam agents.

The ash-producing detergents are exemplified by oil-soluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, or organic phosphorus acids characterized by at leastone direct carbon-to-phosphorus linkage such as those prepared by thetreatment of an olefin polymer (e.g., poly(isobutene) having a molecularweight of 1000) with a phosphorizing agent such as phosphorustrichloride, phosphorus heptasulfide, phosphorus pentasulfide,phosphorus trichloride and sulfur, white phosphorus and a sulfur halide,or phosphorothioic chloride. The most commonly used salts of such acidsare those of sodium, potassium, lithium, calcium, magnesium, strontiumand barium.

The term "basic salt" is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. The commonly empolyed methods for preparing the basic saltsinvolve heating a mineral oil solution of an acid with a stoichiometricexcess of a metal neutralizing agent such as the metal oxide, hydroxide,carbonate, bicarbonate, or sulfide at a temperature above 50° C. andfiltering the resulting mass. The use of a "promoter" in theneutralization step to aid the incorporation of a large excess of metallikewise is known. Examples of compounds useful as the promoter includephenolic substances such as phenol, naphthol, C₆ -₂₆ alkylpenols,thiophenol, sulfurized alkylphenol, and condensation products offormaldehyde with a phenolic substance; C₁ -₂₀ alcohols such asmethanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethyleneglycol, stearyl alcohol, and cyclohexyl alcohol; and C₁ -₂₀ amines suchas aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, anddodecylamine. A particularly effective method for preparing the basicsalts comprises mixing an acid with an excess of a basic alkaline earthmetal neutralizing agent and at least one alcohol promoter, andcarbonating the mixture at an elevated temperature such as 60-200° C.

Ashless detergents and dispersants are so called despite the fact that,depending on its constitution, the dispersant may upon combustion yielda non-volatile material such as boric oxide or phosphorus pentoxide;however, it does not ordinarily contain metal and therefore does notyield a metal-containing ash on combustion. Many types are known in theart, and any of them are suitable for use in the lubricants of thisinvention. The following are illustrative:

(1) Reaction products of carboxylic acids (or derivatives thereof)containing at least about 34 and preferably at least about 54 carbonatoms with nitrogen-containing compounds such as amines, organic hydroxycompounds such as phenols and alcohols, and/or inorganic materials.Examples of these "carboxylic dispersants"0 are described in BritishPatent 1,306,529 and in many U.S. Patents, including the following:

    ______________________________________                                        3,163,603      3,351,552                                                                              3,541,012                                             3,184,474      3,381,022                                                                              3,542,678                                             3,215,707      3,399,141                                                                              3,542,680                                             3,219,666      3,415,750                                                                              3,567,637                                             3,271,310      3,433,744                                                                              3,574,101                                             3,272,746      3,444,170                                                                              3,576,743                                             3,281,357      3,448,048                                                                              3,630,904                                             3,306,908      3,448,049                                                                              3,632,510                                             3,311,558      3,451,933                                                                              3,632,511                                             3,316,177      3,454,607                                                                              3,697,428                                             3,340,281      3,467,668                                                                              3,725,441                                             3,341,542      3,501,405                                                                              Re 26,433                                             3,346,493      3,522,179                                                      ______________________________________                                    

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, preferably polyalkylene polyamines. Thesemay be characterized as "amine dispersants" and examples thereof aredescribed, for example, in the following U.S. Patents:

    ______________________________________                                               3,275,554                                                                            3,454,555                                                              3,438,757                                                                            3,565,804                                                       ______________________________________                                    

(3) Products obtained by post-treating the carboxylic or aminedispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhdyrides, nitriles, epoxides, boron compounds, phosphrous compounds orthe like. Exemplary materials of this kind are described in thefollowing U.S. Patents:

    ______________________________________                                        3,036,003      3,367,943                                                                              3,579,450                                             3,087,936      3,373,111                                                                              3,591,598                                             3,200,107      3,403,102                                                                              3,600,372                                             3,216,936      3,442,808                                                                              3,639,242                                             3,254,025      3,455,831                                                                              3,649,229                                             3,256,185      3,455,832                                                                              3,649,659                                             3,278,550      3,493,520                                                                              3,658,836                                             3,280,234      3,502,677                                                                              3,697,574                                             3,281,428      3,513,093                                                                              3,702,757                                             3,282,955      3,533,945                                                                              3,703,536                                             3,312,619      3,539,633                                                                              3,704,308                                             3,366,569      3,573,010                                                                              3,708,522                                             ______________________________________                                    

(4) Interpolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates oracrylamides and poly-(oxyethylene)-substituted acrylates. These may becharacterized as "polymeric dispersants" and examples thereof aredisclosed in the following U.S. Patents:

    ______________________________________                                               3,329,658                                                                            3,666,730                                                              3,449,250                                                                            3,687,849                                                              3,519,565                                                                            3,702,300                                                       ______________________________________                                    

The pertinent disclosures of all of the above-noted patents areincorporated by reference herein.

Extreme pressure agents and corrosion-inhibiting andoxidation-inhibiting agents are exemplified by chlorinated aliphatichydrocarbons such as chlorinated wax; organic sulfides and polysulfidessuch as benzyl disulfide, bis-(chlorobenzyl)disulfide, dibutyltetrasulfide, sulfurized methyl ester of oleic acid, sulfurizedalkylphenol, sulfurized dipentene, and sulfurized terpene;phosphosulfurized hydrocarbons such as the reaction product of aphosphorus sulfide with turpentine or methyl oleate; phosphorus estersincluding principally dihydrocarbon and trihydrocarbon phosphites suchas dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentylphenyl phosphite, dpentyl phenyl phosphite, tridecyl phosphite,distearyl phosphite, dimethyl naphthly phosphite, oleyl 4-pentylphenylphosphite, polypropylene (molecular weight 500)-substituted phenylphosphite, diisobutyl-substituted phenyl phosphite; metalthiocarbamates, such as zinc dioctyldithiocarbamate, and bariumheptylphenyl dithiocarbamate; Group II metal phosphorodithioates such aszinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate,barium di (heptylphenyl)phosphorodithioate, cadmiumdinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acidproduced by the reaction of phosphorus pentasulfide with an equimolarmixture of isopropyl alcohol and n-hexyl alcohol.

The fuel compositions of the present invention contain a majorproportion of a normally liquid fuel, usually a hydrocarbonaceouspetroleum distillate fuel such as motor gasoline as defined by ASTMSpecification D-439-73 and diesel fuel or fuel oil as defined by ASTMSpecification D-396. Normally liquid fuel compositions comprisingnon-hydrocarbonaceous materials such as alcohol, ethers, organo-nitrocompounds and the like (e.g., methanol, ethanol, diethyl ether, methylethyl ether, nitromethane) are also within the scope of this inventionas are liquid fuels derived from vegetable or mineral sources such ascorn, alfalfa, shale and coal. Normally liquid fuels which are mixturesof one or more hydrocarbonaceous fuels and one or morenon-hydrocarbonaceous materials are also contemplated. Examples of suchmixtures are combinations of gasoline and ethanol, diesel fuel andether, gasoline, and nitromethane, etc. Particularly preferred isgasoline, that is, a mixture of hydrocarbons having an ASTM boilingpoint of 60° C. at the 10% distillation point to about 205° C. at the90% distillation point.

Generally, these fuel compositions contain an amount of the compositionsof this invention sufficient to impart anti-rust, anti-corrosion and/ordispersant and detergent properties to the fuel; usually this amount isabout 1 to about 10,000, preferably 4 to 1,000, parts by weight of thereaction product per million parts by weight of fuel. The preferredgasoline-based fuel compositions generally exhibit excellent engine oilsludge dispersancy and detergency properties. In addition, they exhibitanti-rust and corrosion-preventing properties.

The fuel compositions of this invention can contain, in addition to thecompositions of this invention, other additives which are well known tothose of skill in the art. These can include anti-knock agents such astetra-alkyl lead compounds, lead scavengers such as halo-alkanes (e.g.,ethylene dichloride and ehtylene dibromide), deposit preventors ormodifiers such as triaryl phosphates, dyes, cetane improvers,anti-oxidants such as 2,6-di-tertiarybutyl-4-methylphenol, rustinhibitors, such as alkylated succinic acids and anhydrides,bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers,upper cylinder lubricants, anti-icing agents and the like.

In certain preferred fuel compositions of the present invention, theafore-described compositions of this invention are combined with otherashless dispersants in gasoline. Such ashless dispersants are preferablyesters of a mono- or polyol and a high molecular weight mono- orpolycarboxylic acid acylating agent containing at least 30 carbon atomsin the acyl moiety. Such esters are well known to those of skill in theart. See, for example, French Patent No. 1,396,645, British Patents Nos.981,850 and 1,055,337 and U.S. Pat. Nos. 3,255,108; 3,311,558;3,331,776; 3,346,354; 3,522,179; 3,579,450; 3,542,680; 3,381,022;3,639,242; 3,697,428; 3,708,522; and British Patent Specification1,306,529. These patents are expressly incorporated herein by referencefor their disclosure of suitable esters and methods for theirpreparation. Generally, the weight ratio of the compositions of thisinvention to the aforesaid ashless dispersants is about 0.1 to about10.0; preferably about 1 to about 10 parts of composition of thisinvention to 1 part ashless dispersant.

In still another embodiment of this invnetion, the inventive additivesare combined with Mannich condensation products formed from substitutedphenols, aldehydes, polyamines, and amino pyridines. Such condensationproducts are described in U.S. Pat. Nos. 3,649,659; 3,558,743;3,539,633; 3,704,308; and 3,725,277.

The compositions of this invention can be added directly to the fuel orlubricating oil to form the fuel and lubricant composition of thisinvention or they can be diluted with a substantially inert, normallyliquid organic solvent/diluent such as mineral oil, xylene, or anormally liquid fuel as described above, to form an additive concentratewhich is then added to the fuel or lubricating oil in sufficient amountsto form the inventive fuel and lubricant composition described herein.These concentrates generally contain about 20 to about 90 percent of thecomposition of this invention and can contain in addition any of theabove-described conventional additives, particularly the afore-describedashless dispersants in the aforesaid proportions. The remainder of theconcentrate is the solvent/diluent.

As well as serving as additives in and of themselves, the compositionsof this invention can be post-treated with a variety of chemicalreagents to form post-treated compositions which are also useful asadditives in the aforedescribed fuels and lubricants. These post-treatedadditives are used in concentrations having the same general ranges setforth above and can also be formulated into concentrated as describedabove. They can also be used with the compatible auxiliary additivesalready described.

When the compositions of this invention are to be used in post-treatmentreactions, it is preferred that they are free carboxylic acids,anhydrides, esters of lower alcohols, carboxamides of ammonia, lowermonoamines and carboxylates of ammonia, lower monoamines or metals,especially Group IA, IIA and IIB metals. The post-treatment reagentsinclude the above-described higher mono- and polyhydric alcohols,especially the higher polyhydric alcohols and the above-describedpolyamines and hydroxy polyamines, especially the alkylene polyamines.Mixtures of these post-treating reagents can also be used. Particularlypreferred are mixtures of the afore-described polyhydric triols andtetraols with the afore-described ethylene polyamines.

Reaction of the composition of this invention with the afore-describedpost-treating reagents is carried out under the same general conditionsset forth hereinabove for reactions used to form the carboxylic acidreagents described above. Similarly, the general proportions set forthfor forming the carboxylic acid reagent can be used in the post-treatingreactions, thus, an equivalent of the composition of this invention canbe reacted with 1-5 equivalents of the afore-described post-treatingreagents. An equivalent of the composition of this invention is definedas its molecular weight divided by the number of carboxylic acid groupscontained therein, i.e., carboxylic acid, anhydride ester, carboxamide,carboxylate group. An equivalent of a metallic post-treating reagent isits molecular weight or atomic weight divided by the valence. Thus,sodium, lithium, potassium, etc. have equivalent weights equal to theiratomic weights while calcium, zinc and barium, etc., have equivalentweights which are half their atomic weights. The equivalent weight of apolyamine or polyhydric alcohol is its molecular weight divided by thenumber of hydroxyl and/or amino groups present.

The oils described hereinabove are particularly useful insolvent/diluents for post-treatment reactions, although the reactionscan also be carried out without the presence of a solvent/diluent or inthe presence of a solvent/diluent such as the relatively low boilingorganic liquids set forth hereinabove in relation to the reactions usedto form the carboxylic acid reagents.

The compositions of this invention can also be post-treated with a threeand four membered ring heterocyle compound such as epoxides,episulfides, ethylene amines, oxytanes, azetanes, etc. Suchpost-treating reagents have the general formula ##STR12## wherein thecircle represents a chain of 2 to 3 carbon atoms and X represents anoxygen, sulfur or NQ group, Q being a hydrogen or a C₁ -₃₀hydrocarbon-based group. Each of the carbon atoms in the circle can besubstituted with hydrogen or a Q group as defined above, preferably,however, they are substituted with hydrogen and/or a single methyl groupas in ethylene oxide, propylene oxide, etc. Post-treatments with the 3and 4 membered ring heterocyle can be carried out in conditions wellknown to those of skill in the art. Generally, such post-treatmentsoccur at temperatures between 0° C. and about 120° C. Preferably, theyare carried out at temperatures of 15° C. to about 40° C. Suchpost-treatment and reactions can be carried out in a period as short asabout 0.1 hour or as long as about 48 hours. Preferably, they arecarried out in a period of about 1 to about 10 hours. At least about 0.5mole to about 20 moles of heterocycle per equivalent of the compositionof this invention is used in these post-treatment reactions. It is alsopossible to use mixtures of the 3 and 4 membered ring heterocylicpost-treating reagents and mixtures of these heterocycle reagents withother post-treating reagents described hereinbefore.

Post-treatments of the products of this invention can also be carriedout with reagents such as elemental sulfur, carbon oxy sulfide or carbondisulfide. Such post-treatments are carried out under the same generalconditions as described hereinbefore with small ring heterocyclepost-treatments and involve the same reactant proportions as the latter.

Compositions of this invention can also be overbased with Group IA, IIAand IIB basically reacting methyl compounds. Especially preferredcompositions for such overbasing are those compositions containing afree carboxylic acid group or carboxylate metal or ammonium salt groups,and a hydroxyl group attached directly to an aromatic nucleus. Thesematerials are analogous to the well-known overbased salicylate, whichare described in U.S. Pat. No. 3,567,637; U.S. Pat. No. 2,258,591; andU.S. Pat. No. 2,252,662. Generally, the overbased compositions are madeby reacting a carboxylate or carboxylic acid made according to thisinvention with a basically reacting metal oxide, hydroxide, alkoxide orphenoxide in the presence of an inorganic acidic material such as, forexample, CO₂, SO₂, H₂ S, HCl, etc. and a promotor such as, for example,water, lower alcohols and phenols, fatty carboxylic acids (e.g., aceticacid) and their salts and lower ketones and aldehydes. Generally, theseoverbasing reactions are carried out between about 25 and about 150° C.for about 0.25 to about 25 hours using about 2.5 to 30 moles ofbasically reacting metal compound to each equivalent of carboxylcompound (as defined hereinabove).

Further details as to making these overbased materials are generallyknown to those skilled in the art as is shown in the above-notedpatents. Therefore, these patents are incorporated by reference fortheir teachings of how to overbase carboxylic acid compounds.

The following are examples of lubricating oil, fuel oil and concentratecompositions containing the compositions of this invention.

EXAMPLE A

A lubricating oil composition containing 2.5% of the oil solutiondescribed in Example 5.

EXAMPLE B

A gasoline suitable for use in automotive engines containing in additionto the conventional dye and antiknock compounds, 0.001% of the oilsolution described in Example 7.

EXAMPLE C

A diesel fuel containing in addition to a conventional anti-oxidantadditive, 0.5% of the oil solution described in Example 5.

EXAMPLE D

A lubricating oil composition for gasoline engines graded 10W-40according to SAE standards and having as a base oil a mixture of asolvent-refined 100 neutral and solvent-refined 200 neutral oil in equalamounts by volume and containing the following additives:

    ______________________________________                                        Additive               Amounts                                                ______________________________________                                        Polymeric VI Improver  13% *                                                  Zinc Dithiophosphate   1.3%                                                   Over-based Magnesium Sulfonate                                                                       0.9%                                                   Phenolic Anti-oxidant  1.0% *                                                 Sulfurized hydrocarbon E.P. Agent                                                                    0.3% *                                                 Ethoxylated Surfactant 0.3% *                                                 Carboxylic Acid Rust Inhibitor                                                                       0.1% *                                                 Silicone Anti-foamant  100 ppm                                                Oil Solution Described in Example 19                                                                 5.5%                                                   ______________________________________                                        The balance of the lubricant composition is the base oil.                      * % by volume                                                            

EXAMPLE E

An additive concentrate suitable for formulating additive packages foruse in fuels and lubricants comprising 50% of the oil solution ofExample 19 and 50% of the base oil described in Example D.

What is claimed is:
 1. An overbased metal carboxylate made by reactingat least one basically reacting metal compound in the presence of apromoter and an acidic reagent with at least one composition made byreacting (I) at least one phenoxide metal salt of a bridged phenolhaving (a) at least 2 and up to about 20 phenolic moieties or thiophenolanalogs thereof and (b) at least 1 and up to about 19 bridging linkagesindependently selected from the group consisting of covalentcarbon-to-carbon single bonds, ether linkages, sulfide linkages,polysulfide linkages of two to six sulfur atoms, sulfinyl linkages,sulfonyl linkages, methylene linkages, alkylene linkages, di(loweralkyl)methylene linkages, lower alkylene ether linkages, lower alkylenesulfide linkages, lower alkylene polysulfide linkages of two to sixsulfur atoms, amino linkages, polyamino linkages and mixtures of saiddivalent bridging linkages with (II) at least one carboxylic acidreagent having 1 to about 3 carboxyl-based groups and ahalogen-substituted hydrocarbon-based aliphatic or alicyclic groupcontaining a halogen atom.
 2. An overbased carboxylate composition asclaimed in claim 1 wherein one or more of the phenolic phenol moietiesare substituted with 1 to 3 hydrocarbon-based aliphatic or alicyclicgroups from 1 to about 300 carbon atoms.
 3. An overbased carboxylatecomposition as claimed in claim 2 wherein the phenoxide metal salt is ofa Group IA, Group IIA, Group IIIA, Group IB or Group IIB metal ormixtures thereof.
 4. An overbased carboxylate composition as claimed inclaim 3 wherein the hydrocarbon-based group is purely hydrocarbyl andcontains at least about 30 and up to about 250 carbon atoms.
 5. Anoverbased carboxylate composition as claimed in claim 1 wherein thecarboxylic acid reagent (II) is of the formula

    A-(Cox).sub.1-3

wherein A represents a halogen-bearing hydrocarbon-based aliphatic oralicyclic group of 1 to about 20 carbon atoms and each Cox independentlyrepresents a member selected from the group consisting of carboxylic,carboxyl and carboxamide.
 6. An overbased carboxylate composition asclaimed in claim 3 wherein the carboxylic acid reagent (II) is of theformula

    A-(Cox).sub.1 -.sub.3

wherein A represents a halogen-bearing hydrocarbon-based aliphatic oralicyclic group of 1 to about 20 carbon atoms and each Cox independentlyrepresents a member selected from the group consisting of carboxylic,carboxyl and carboxamide.
 7. An overbased carboxylate composition asclaimed in claim 6 wherein the halogen is chlorine or bromine, the groupCox is selected from the group consisting of carboxylates of Group IAmetals, carboxylic esters of lower alkanols, carboxamides of lower alkylmono-amines and ammonia, and carboxylates of lower alkyl mono-amines. 8.An overbased carboxylate composition as claimed in claim 7 wherein thecarboxylic acid reagent (II) is an ester of chloroacetic acid or a GroupIA metal chloroacetate.
 9. An overbased metal carboxylate made byreacting at least one basically reacting metal compound in the presenceof a promoter and an acidic reagent with at least one composition madeby reacting (I) at least one phenoxide metal salt of a bridged phenol ofthe general formula ##STR13## wherein n, n' and n" are eachindependently integers of 1-3; R, R' and R" are each independentlyaliphatic hydrocarbon-based groups of one to about 300 carbon atomseach; m, m' and m" are each independently integers of 0-3; N is aninteger of 0-20 and each X is a divalent bridging linkage selected fromthe group consisting of covalent carbon-to-carbon single bonds, etherlinkages, sulfide linkages, polysulfide linkages of two to six sulfuratoms, sulfinyl linkages, sulfonyl linkages, methylene linkages,alkylene linkages, di(lower)methylene linkages, lower alkylene etherlinkages, lower alkylene sulfide linkages, lower alkylene polysulfidelinkages of two to six sulfur atoms, amino linkages, polyamino linkagesand mixtures of said divalent bridging linkages, with (II) at least onecarboxylic acid reagent of the formula

    A-(Cox).sub.1 -.sub.3

wherein A represents a hydrocarbon-based aliphatic or alicyclic groupcontaining at least one halogen atom and 1 to about 20 carbon atoms,each Cox independently representing a carboxyl-based group.
 10. Acomposition as claimed in claim 9 wherein (I) is a salt of a Group IA orIIA metal, the bridging linkage X is a methylene linkage, sulfidelinkage, methylene ether linkage or polysulfide linkage, the R groupsare all the same, m, m' and m", n, n' and n" are each 1, the halogen ischlorine or bromine, and the group Cox is selected from the groupconsisting of carboxylates of Group IA and IIA metals, carboxylic estersof lower alkanols, carboxamides of lower alkyl mono-amines and ammoniaand carboxylates of lower alkyl mono-amines and ammonia.
 11. A lubricantcomposition comprising a major amount of at least one oil of lubricatingoil viscosity and a minor amount of the composition claimed in claim 1.12. A lubricant composition comprising a major amount of at least oneoil of lubricating oil viscosity and a minor amount of the compositionclaimed in claim
 2. 13. A lubricant composition comprising a majoramount of at least one oil of lubricating oil viscosity and a minoramount of the composition claimed in claim
 3. 14. A lubricantcomposition comprising a major amount of at least one oil of lubricatingoil viscosity and a minor amount of the composition claimed in claim 4.15. A lubricant composition comprising a major amount of at least oneoil of lubricating oil viscosity and a minor amount of the compositionclaimed in claim
 5. 16. A lubricant composition comprising a majoramount of at least one oil of lubricating oil viscosity and a minoramount of the composition claimed in claim
 6. 17. A lubricantcomposition comprising a major amount of at least one oil of lubricatingoil viscosity and a minor amount of the composition claimed in claim 7.18. A lubricant composition comprising a major amount of at least oneoil of lubricating oil viscosity and a minor amount of the compositionclaimed in claim
 8. 19. A concentrate comprising about 10 to about 90percent of the composition claimed in claim 1 and a normally liquidorganic solvent/diluent.
 20. A concentrate comprising about 10 to about90 percent of the composition claimed in claim 3 and a normally liquidorganic solvent/diluent.
 21. A concentrate comprising about 10 to about90 percent of the composition claimed in claim 9 and a normally liquidorganic solvent/diluent.